CN108137837B - Method for producing a composite conductive material and composite material obtained with this method - Google Patents

Method for producing a composite conductive material and composite material obtained with this method Download PDF

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CN108137837B
CN108137837B CN201680059680.1A CN201680059680A CN108137837B CN 108137837 B CN108137837 B CN 108137837B CN 201680059680 A CN201680059680 A CN 201680059680A CN 108137837 B CN108137837 B CN 108137837B
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particles
polymer matrix
composite
electrically conductive
coating
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CN108137837A (en
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M.奥德内尔特
D.胡泽
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Arkema France SA
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
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    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/026—Knitted fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B64—AIRCRAFT; AVIATION; COSMONAUTICS
    • B64D—EQUIPMENT FOR FITTING IN OR TO AIRCRAFT; FLIGHT SUITS; PARACHUTES; ARRANGEMENTS OR MOUNTING OF POWER PLANTS OR PROPULSION TRANSMISSIONS IN AIRCRAFT
    • B64D45/00—Aircraft indicators or protectors not otherwise provided for
    • B64D45/02—Lightning protectors; Static dischargers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/14—Mixture of at least two fibres made of different materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/02—Synthetic macromolecular particles
    • B32B2264/0214—Particles made of materials belonging to B32B27/00
    • B32B2264/0264—Polyamide particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/212—Electromagnetic interference shielding
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2605/18—Aircraft
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material

Abstract

The present invention relates to a process for producing an electrically conductive composite material, and to a composite material obtainable by said process. The conductive material is obtained from a composite polymer matrix formed by the aggregation of composite conductive particles consisting of particles of the polymer matrix having a diameter d50 of 1-4000 μm, coated with a layer of conductive material consisting of at least one metal. The ratio of the thickness of the conductive layer to the d50 diameter of the polymer matrix particles is from 0.0025:100 to 1.5:100, the thickness being less than 300 nm.

Description

Method for producing a composite conductive material and composite material obtained with this method
Technical Field
The present invention relates to a method for manufacturing an electrically conductive composite material, and also to a composite material obtainable by this method.
Background
Polymeric materials have certain advantages in many applications due to the lightweight (light) nature of the polymer. Their mechanical properties can also be adjusted by incorporating various fillers and in particular reinforcing fibers such as carbon fibers therein. The composite material thus obtained advantageously replaces metals in many applications. Thus, it is estimated that composite materials currently account for more than 25% of the weight of the airbus a380 structure, where the composite material replaces the aluminum alloy in the airbus a 380.
However, the electrical conductivity of these carbon fiber-based composites is much lower than that of metals. In particular, these fibers have the disadvantage of forming conductive paths in the material based on their orientation. This drawback is particularly pronounced in the context of layered structures commonly used in the aeronautical field, which have an insufficient capacity to dissipate electric currents in a direction perpendicular to the plane of the fibrous layers, the electrical conductivity in this direction typically being close to that of non-conductive polymers. Therefore, these structures are not sufficiently resistant to lightning (lightning). In fact, an aircraft struck by lightning must be able to flow out (drain off) and therefore conduct about 10 a5Ampere current without excessive potential differences that can cause delamination of the composite structure and serious damage to the on-board electronics. It is therefore necessary to improve the conductivity of these structures so that the conductivity approaches that of copper or aluminum in the stacking direction of the layers.
In order to overcome the above drawbacks, it has been proposed to disperse conductive particles in a polymer matrix intended to impregnate carbon fibres (EP2371529 and EP 2687557). These conductive particles are intended to form an electrical bridge (electrical bridges) on either side of the resulting composite. They may be formed from glass or PMMA particles coated with a conductive metal, or a carbon-based material, such as carbon black. In addition to the handling problems inherent with the use of nanofillers such as carbon black, these conductive particles are difficult to disperse uniformly in the polymer matrix due to their different densities from the molten polymer. Thus, the inclusion of these particles in a polymer matrix may complicate the formulation of the latter. Furthermore, the amount of filler required to reach the percolation threshold (above which the composite is electrically conductive) may negatively impact certain mechanical properties of the material.
Other polymer matrices incorporating composite conductive particles of the core-shell type are described in documents US-5,965,064 and US 2012/279781. The use of core-shell type conductive composite particles in the formulation of conductive metal arrays is further described in the literature by Brodoceanu et al in Nanotechnology, vol.24, No.8(February 5, 2013).
The development of polymer-based conductive composites also has advantages in industrial contexts outside aviation, and in particular in the manufacture of housings for protecting electronic devices from electrostatic charges.
In the search for solutions aimed at making the polymer matrix electrically conductive, it has been suggested to incorporate carbon nanotubes therein. These fillers have more significant dispersion problems than the conductive fillers discussed above due to their intertwined structure. Furthermore, although the concentration of nanotubes required to reach the percolation threshold is lower than that of other fillers, the nanotubes at this concentration have a tendency to increase the viscosity of the matrix which affects the flow properties required for its handling (processing) and here also limits its formulation.
The aforementioned dispersion problems can be overcome and the electrical conductivity of the composite material increased by applying carbon nanotubes or carbon black around the polymer particles in order to form conductive composite particles that are subsequently aggregated into a conductive composite without dispersing these fillers in the polymer matrix. Hao et al therefore propose in Materials Chemistry and Physics, vol.109, 15-19(2008) a particular process for coating polyethylene particles with Carbon Nanotubes (CNTs) or carbon black, which is carried out under conditions that cause the polymer particles to soften and the filler to adhere to their surface. The composite particles obtained are then compression molded to form a panel.
Although it has certain advantages, this method does not eliminate the problem of handling the nanofiller and its possible impact on the environment. Therefore, there remains a need to provide an alternative to the above described methods.
Disclosure of Invention
In the present invention, the inventors have developed a method of making a composite using metal-coated polymer particles that does not require the dispersion of these particles in a polymer matrix. Although the process and the particles used have some similarities to those described by Hao et al, the difference between them lies in the fact that: the composite particle surface of Hao et al consists of aggregates of entangled CNTs or aggregated carbon black particles, rather than a continuous film. The research carried out by the applicant has made it possible to adjust the properties of the composite particles and the steps of the method according to the invention so as to make it possible to reconcile the two previously conflicting requirements for metal-type composite particles, namely the use of a sufficient quantity of metal to reach the percolation threshold, without however preventing the agglomeration (coalescence) of the polymer particles above the melting point. Furthermore, the method according to the invention has the advantage that the mechanical properties of the polymer are not substantially changed during the formation of the composite material. Finally, it makes it possible to eliminate the formulation limitations of the polymer matrix assisted by the additives of the prior art.
The object of the present invention is therefore to provide an electrically conductive composite obtained from a polymer matrix, which, when in the form of a sheet, provides good transverse electrical conductivity, and good mechanical properties, while being easy to manufacture.
One subject of the present invention is therefore a method for manufacturing an electrically conductive composite material from a composite polymer matrix, wherein the composite polymer matrix is formed by aggregating electrically conductive composite particles consisting of particles of the polymer matrix, the particles of the polymer matrix having a d50 diameter of 1-4000 μm, coated with a layer of an electrically conductive material, the particles not being dispersed in the polymer matrix, characterized in that the electrically conductive material consists of at least one metal and in that the ratio of the thickness of the layer to the d50 diameter of the polymer matrix particles measured according to standard ISO9276 is between 0.0025:100 and 1.5:100, the thickness being less than 300 nm.
Another subject of the invention is a composite material that can be obtained according to the above method, advantageously comprising a composite polymeric matrix containing a three-dimensional metallic network forming continuous conductive paths.
Detailed Description
The method of manufacturing the composite material according to the present invention is characterized in that it includes a step of aggregating the conductive composite particles (consists in).
These particles may have a spherical, spheroidal or aspherical shape. The diameter of these particles may be between 1 and 4000. mu.m, preferably between 5 and 1000. mu.m, more preferably between 10 and 500. mu.m, for example between 30 and 300. mu.m.
In the context of the present invention, the term "diameter" is used to describe the diameter of the circumscribed circle of a particle. D50 corresponds to the value of the particle size (particle size) that accurately divides the particle population being examined into two. In other words, 50% of the particles have a size less than the D50. D50 was measured according to the standard ISO 9276-part 1 to 6: "statement of results of particle size analysis (reproduction of results of particle size analysis)". In the present invention, a laser particle size analyzer (e.g., Malvern type) is used to obtain the particle size distribution of the powder and infer D50 therefrom.
In addition, in the specification of the present invention, the expression "between" means an interval including the mentioned end points.
The electrically conductive composite particles used according to the invention consist of a core formed by a polymer matrix coated with a shell of at least one electrically conductive metal. They do not contain any further layers, in particular layers outside the shell, such as polymer layers.
The polymer matrix comprises at least one thermoplastic or thermosetting polymer, which may optionally have elastomeric properties, preferably one or more thermoplastic, advantageously non-elastomeric polymers.
Examples of thermoplastic polymers include homopolymers and copolymers of olefins such as acrylonitrile-butadiene-styrene copolymer, polyethylene, polypropylene, polybutadiene, and polybutylene; vinyl polymers such as poly (divinylbenzene) and ethylene/vinyl acetate copolymers; acrylic homopolymers and copolymers and polyalkyl (meth) acrylates, such as poly (methyl methacrylate); homopolyamides and copolyamides; a polycarbonate; polyesters, including poly (ethylene terephthalate) and poly (butylene terephthalate); polyethers such as poly (phenylene ether) and poly (formaldehyde); polystyrene and styrene/acrylonitrile copolymers; styrene/maleic anhydride copolymers; poly (vinyl chloride); fluoropolymers such as polyvinylidene fluoride, polytetrafluoroethylene, and polychlorotrifluoroethylene; a thermoplastic polyurethane; polyether ether ketone (PEEK) and polyether ketone (PEKK); a polyetherimide; polysulfones; poly (phenylene sulfide); cellulose acetate; and mixtures thereof.
According to a preferred mode of carrying out the invention, the polymer is chosen from polyamides and polyketones.
Polyamides include homopolyamides and copolyamides.
Among the homopolyamides (PA), mention may be made in particular of PA-6, PA-11 and PA-12 obtained by polymerizing amino acids or lactams, PA-6.6, PA-4.6, PA-6.10, PA-6.12, PA-6.14, PA6-18, PA-10.10 and PA-10.12 obtained by polycondensation of diacids and diamines, and also aromatic polyamides, such as polyarylamides, in particular obtained from 1, 3-xylylenediamine and/or 1, 4-xylylenediamine, and polyphthalamides, obtained from terephthalic acid and/or isophthalic acid. Some of the foregoing polymers are available from ARKEMA, particularly under the tradename RILSAN.
Copolyamides are obtainable from various starting materials: (i) lactam, (ii) aminocarboxylic acid or (iii) equimolar amounts of diamine and dicarboxylic acid. The formation of copolyamides requires the selection of at least two different starting products from those described above. The copolyamide then comprises at least these two moieties. It may thus relate to aminocarboxylic acids and lactams having a different number of carbon atoms, or two lactams having different molecular weights, or lactams in combination with equimolar amounts of diamine and dicarboxylic acid. The lactam (i) may be chosen in particular from lauryllactam and/or caprolactam. The aminocarboxylic acid (ii) is advantageously chosen from alpha, omega-aminocarboxylic acids, such as 11-aminoundecanoic acid or 12-aminododecanoic acid. For precursor (iii), this may in particular be at least one C6-C36Aliphatic, alicyclic or aromatic dicarboxylic acids with at least one C4-C22Combinations of aliphatic, cycloaliphatic, arylaliphatic or aromatic diamines such as adipic acid, azelaic acid, sebacic acid, brassylic acid, n-dodecanedioic acid, terephthalic acid, isophthalic acid or 2, 6-naphthalenedicarboxylic acid, and diamines such as hexamethylenediamine, piperazine, 2-methyl-1, 5-diaminopentane, m-xylylenediamine or p-xylylenediamine, it being understood that the 11 dicarboxylic acids and diamines, when present, are used in equimolar amounts. Such copolyamides are in particular under the trade name
Figure BDA0001626267160000041
Sold by ARKEMA.
According to one embodiment of the invention, as polyamide, a semi-aromatic (based on aromatic structures) and/or semi-cycloaliphatic (based on cycloaliphatic structures) polyamide can be chosen, preferably semi-aromatic, more particularly corresponding to the following formula:
polyamides comprising x.T units wherein x is C9To C18Preferably C9、C10、C11、C12A linear aliphatic diamine and wherein T is terephthalic acid selected from the group consisting of 8.T, 9.T, 10.T, 11.T, 12.T, 6.T/9.T, 9.T/10.T, 9.T/11.T, 9.T/12.T, 9/6.T, 10/6.T, 11/6.T, 12/6.T, 10/9.T, 10/10.T, 10/11.T, 10/12.T, 11/9.T, 11/10.T, 11/11.T, 11/12.T, 12/9.T, 12/10.T, 12/11.T, 12/12.T, 6.10/6.T, 6.12/6.T, 9.10/6.T, 9.12/6.T, 10.10/6.T, 10.12/6.T, 6.10/9.10/6. T, 9.9.10/9.9.9.9/9. T, 9.10/9.9.9.9.9/10/6. T, 10T, 10/6.T, 10/6.T, 6.T, 9, and a, 10.12/9.T, 6.10/10.T, 6.12/10.T, 9.10/10.T, 9.12/10.T, 10.10/10.T, 10.12/10.T, 6.10/12.T, 6.12/12.T, 9.10/12.T, 9.12/12.T, 10.10/12.T, 11/6.T/9.T, 11/6.T/10.T, 11/6.T/11.T, 11/6.T/12.T, 11/9.T/10.T, 11/9.T/11.T, 11/9.T/12.T, 11/10.T/11.T, 11/10.T/12.T, 11/11.T/12.T, 6.T/10.T, 6.T/11. T/12.T, 10.T, 11/12.T, 10.T, 10.T, T/12.T, 10.T, 10.T, T/12.T, 10.T, 10.T, 10.T, 12, T, 12, T, 10, T, 12, T, 12, T, 12, T, 12, T, 9, 12, T, 12, T, 12, T, 9, 12/6.T/11.T, 12/6.T/12.T, 12/9.T/10.T, 12/9.T/11.T, 12/9.T/12.T, 12/10.T/11.T, 12/10.T/12.T, 12/11.T/12.T,
-the previous terpolymer polyamide wherein 12/is replaced by 9/, 10/, 6.10/, 6.12/, 10.10/, 10.12/, 9.10/and 9.12/,
all the polyamides mentioned above in which terephthalic acid (T) is partly or completely replaced by isophthalic acid (I), by naphthalene-2, 6-dicarboxylic acid and/or by 1, 3-or 1,4-CHDA (cyclohexanedicarboxylic acid), in which all or some of the aliphatic diamines may be replaced by cycloaliphatic diamines,
all of the above polyamides, wherein C6-C12Aliphatic diamines replaced by cycloaliphatic diamines from BMACM, BACM and/or IPDA and partly or wholly aromatic diacids T by straight-chain or branched C6-C18Aliphatic dibasic acids.
In the inventionIn an advantageous embodiment, as thermoplastic polymer a semi-crystalline polyamide is used having a glass transition temperature of at least 100 ℃, preferably at least 120 ℃, and a melting point below 280 ℃, these temperatures being measured by DSC according to standard ISO 11357. The polyamide preferably has the general formula 10.T/A.T, wherein T represents terephthalic acid and A represents, for example, m-xylylenediamine (MXDA) or 2-methylpentamethylenediamine (MPMDA). The polyamide can be obtained from a reactive composition of at least one prepolymer, which is a precursor of said polyamide, bearing two terminal functional groups (generally NH) that co-react with each other by condensation 2And COOH) or two identical terminal functional groups (typically NH)2Or COOH) capable of being mixed with another prepolymer (usually COOH or NH) mixed therewith2) The supported terminal functional groups react. As a variant, the polyamide may be obtained by incorporating two
Figure BDA0001626267160000051
Obtained by mixing said precursors in the presence of a monomeric chain extender of terminal functional groups of the oxazoline, epoxy resin or isocyanate type.
As thermosetting polymers, epoxy resins, unsaturated polyesters, phenolic resins, melamine-formaldehyde resins and polyimides can be used in particular, provided that they are in solid form at ambient temperature (25 ℃). Epoxy resins are preferred for use in the present invention.
In addition to the above polymers, the polymer matrix used according to the invention may further optionally contain one or more additives selected from the group consisting of: conductive fillers, curing agents, plasticizers, lubricants, pigments, dyes, UV stabilizers, antioxidants and/or heat stabilizers, impact modifiers, reinforcing fillers, antistatic agents, fungicides, flame retardants and mixtures thereof. According to one preferred method of carrying out the invention, it contains expanded graphite intended to improve its thermal conductivity. Reinforcing fillers are particulate materials in the form of inclusions (inclusions) or fibers, which aim at improved matrix properties. Ceramic, organic, inorganic and metallic fibers and carbon nanotubes constitute examples of such materials. It is preferred according to the invention for the polymer matrix to contain one or more electrically conductive fillers, such as graphite.
As mentioned above, the particles used according to the invention are coated with a layer of a metallic type conductive material.
Examples of the metal that can be used in the present invention include silver, gold, nickel, copper, platinum, tin, titanium, cobalt, zinc, iron, chromium, aluminum, and alloys thereof, preferably gold, silver, nickel, copper, platinum, tin, and titanium, and more preferably silver.
The application of the metal coating to the polymer particles can be performed by a variety of methods, such as Physical Vapor Deposition (PVD), Chemical Vapor Deposition (CVD), and autocatalytic deposition (electroless plating). In the present invention, the conductive composite particles are preferably obtained by vapor deposition of at least one metal on the surface of the polymer base particles. In a CVD process, the organometallic compound can be heated to enter a vapor state and then entrained in a fluidized bed reactor containing polymer particles to decompose the organometallic precursor and deposit the metal on the polymer particles. The process temperature and time, as well as the amount of precursor, allow control of the thickness of the deposit. In PVD processes, metal precursors of the metal to be deposited can be evaporated by electron bombardment, joule effect, induction, electric arc or ion beam. As a variant, the metal may be deposited by vacuum sputtering or by ion deposition. The skilled person will know how to adjust the parameters of these processes to obtain a metal layer with a desired thickness. A CVD process is preferably used in the present invention.
The amount of metal deposited on the polymer matrix particles may represent from 1% to 25% by weight, preferably from 5% to 20% by weight, relative to the total weight of the particles, provided that the thickness of the metal layer is less than 300nm, as measured according to techniques well known to the person skilled in the art, for example by means of electron microscopy after ion polishing, and provided that the ratio of the thickness of the layer to the d50 diameter of the polymer matrix particles measured according to standard ISO9276 is between 0.0025:100 and 1.5:100, preferably between 0.005:100 and 1:100, and better still between 0.1:100 and 0.5: 100.
In the process according to the invention, the above-mentioned composite particles are aggregated, preferably by bringing the particles into contact under low shear conditions, at a temperature at which the polymer matrix is at least partially molten, so as to cause coalescence (coalesce) of the particles. A composite polymer matrix containing a three-dimensional metal network forming a continuous conductive path is thus obtained.
Thus, it is preferred not to use a process of compounding, injection molding or extrusion of the composite particles, which results in excessive powder shear.
On the other hand, this agglomeration step can be carried out by any process of manufacturing (additive manufacturing) parts from powder additive material, and in particular laser sintering (SLS) or mask sintering (SMS) or compression moulding of the granules to form a composite material. The composite material may be obtained directly in the desired shape or, where the polymer matrix comprises a thermoplastic polymer, it may be subsequently melted and reshaped.
Alternatively, the method according to the invention may comprise a step of coating the substrate with the above-mentioned composite particles, said step being carried out before or simultaneously with the aggregation step. The substrate is advantageously a fibrous substrate, which may be formed from natural or synthetic fibers such as glass fibers, carbon fibers, metallized polymer fibers, and mixtures thereof. These fibers may be non-woven or woven, braided or knitted in any manner, and may be in the form of, for example, rovings, corduroy (cord), sheets or tapes. In the present invention, the substrate is preferably composed of a sheet of carbon fiber. According to one embodiment, the coating and aggregation steps may be performed simultaneously by fluidized bed dip coating. In this case, the substrate is brought to a temperature above the melting point of the polymer forming the core of the particles before the particles are applied to the surface of the substrate. According to another embodiment, the coating step may be a step of dry impregnation of the substrate, in particular by electrostatic spraying, and the aggregation step may then comprise heat treatment of the impregnated substrate, for example by infrared heating or convection oven.
In the above variants, the composite material obtained constitutes a pre-impregnated substrate, which can be shaped according to various techniques. In particular, when it is in the form of a sheet, it may be reinforced, for example by calendering (consolidate). As a variant, when it is in the form of composite fibers, these fibers can be transformed into a rotating member by filament winding or into a profiled element by pultrusion. Another forming process that may be performed is in a fiber or tape placement (placement) process. The equipment capable of carrying out these processes may comprise coating and heating (accumulation) means which make it possible to carry out all the steps of the method according to the invention.
The pre-impregnated substrate is preferably composed of a layer (ply) composed of a fibrous substrate which is generally covered on both sides with the composite material according to the invention. Several of these layers may be superimposed on a former (mold) to form a laminate (laminate) that is then oven baked. In the case where the conductive composite particles contain a thermosetting resin, the laminate is generally subsequently heated and compressed to cure the resin.
At the end of these steps of optional coating, aggregation and general shaping, a composite material according to the invention is obtained.
It can be used in particular in any application where high electrical conductivity is required, in particular to improve electromagnetic shielding and/or electrostatic protection of electronic components, and can also impart lightning protection to aeronautical components, wind turbines, buildings, motor vehicles, trains or boats. In the field of aeronautics, the composite material according to the invention can be used in particular for the manufacture of fuselages, wings, ailerons, flaps, fairings, webbings, air intakes, radomes or fairings.
Examples
The invention will be better understood from the following examples, which are given purely by way of illustration and are not intended to limit the scope of the invention, as defined by the appended claims.
Example 1 production of composite film
Polyamide 11 (provided by ARKEMA) coated with a layer of silver in a proportion of 8% to 10% by weight (relative to the total weight of the particles) obtained by CVD
Figure BDA0001626267160000081
PA 11). These composite particles D50 were 100 μm in diameter as measured by laser particle size analysis. The thickness of the metal coating is about 150 nm.
These particles were applied to siliconized steel plates up to 330 ° by fluidized bed dip coating. The thickness of the obtained film was 300. mu.m. It was separated from the plate and then analyzed with a scanning electron microscope. Good particle coalescence and the presence of a continuous metal network in the material are observed.
The resistance of the film was then measured by the so-called 4-point method, which consists in plotting the voltage measured as a function of the intensity applied to the sample for four different intensity values. The slope of the line obtained corresponds to the surface resistance of the film, which in this example is 4 ohms. The volume resistivity was 200 ohm-cm.
Example 2 (comparative) composite films were made
A composite film was prepared as in example 1, except that the weight fraction of silver was 15-20% instead of 8-10%. The particles obtained were coated with a layer of silver having a thickness of 300-400 nm.
These films are brittle and have a rough and porous appearance. Observation with a scanning electron microscope showed moderate coalescence of the grains (grains) which further appeared to mix with the metal debris.
Example 3: manufacture of composite board
Four carbon fiber reinforcements (200 g/m) having a width of 195mm and a length of 295mm were prepared by dusting a powder of PA11 granules as described in example 12Hexcel plain 3K HS) on both sides. After the four layers thus obtained were stacked and an adhesive was applied to the four sides of the stack, the stack was subjected to hot pressing. To this end, it was placed in a 200mm wide and 300mm long mould, covered on each side with a teflon-coated fabric sheet, and the mould was then introduced into a muffle (Carver) press, the platens of which were preheated to 290 ℃ and the pressure applied to the layers was 1.7 bar. The temperature of the press plate was then lowered to 250 ℃ and the pressure was brought to 10 bar after 30 seconds. After 15 minutes, the platens were cooled to a temperature of about 100 ℃. And (4) taking out the composite board from the die to obtain the composite board.
The volume resistivity of these sheets was about 3000 ohm-cm in volume, as measured by the so-called four-point method.

Claims (9)

1. A method for manufacturing an electrically conductive composite material from a composite polymer matrix, wherein the composite polymer matrix is formed by aggregation of electrically conductive composite particles consisting of particles of the polymer matrix, the particles of the polymer matrix having a d50 diameter between 1 and 4000 μm, being coated with a layer of an electrically conductive material, the particles being not dispersed in the polymer matrix and being free of any other layer, characterized in that the electrically conductive material consists of at least one metal and in that the ratio of the thickness of the layer to the d50 diameter of the polymer matrix particles measured according to standard ISO9276 is between 0.0025:100 and 1.5:100, the thickness being less than 300 nm.
2. A method according to claim 1, wherein aggregation of the particles is effected by contacting the composite particles under low shear conditions at a temperature at which the polymer matrix is at least partially molten, such that the particles coalesce.
3. The method of claim 2, wherein the agglomeration of the particles is performed by laser sintering, mask sintering, or compression molding of the particles.
4. The method of claim 2, further comprising the step of coating the substrate with said particles prior to or simultaneously with their aggregation.
5. The method of claim 4, wherein the coating and agglomerating steps are performed simultaneously by fluidized bed dip coating.
6. The method of claim 4, wherein the coating step is a dry impregnation step of the substrate and wherein the aggregating step comprises heat treating the impregnated substrate.
7. A method according to any of claims 1 to 6, wherein the polymer matrix comprises one or more thermoplastic polymers.
8. The method according to any one of claims 1 to 6, characterized in that the conductive composite particles are obtained by vapour deposition of at least one metal on the surface of particles consisting of a polymer matrix.
9. Composite material obtainable according to the process of any one of claims 1-8.
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